Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

Silverstein, D.; Govind, Niranjan; Dam, Hubertus J. J. van; Jensen, Lasse

doi:10.1021/ct4007772

Cited by 56 publications

(61 citation statements)

References 130 publications

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“…In this work, we have used TDDFT method with B3LYP functional to determine these signs, and we have also shown in the earlier studies for several nucleobases that the signs of the gradients remain unchanged irrespective of the choice of the DFT functional used . This method of determining the excited state gradients has been used by various groups and is well documented in literature . We also note here that depending upon the specific functional and basis sets used in DFT calculations, the normal mode compositions may also vary slightly which would also impact the computed excited state structural distortions.…”

Section: Resultsmentioning

confidence: 64%

Deep ultraviolet initiated excited state dynamics of riboflavin and flavin mononucleotide

Ghosh

Puranik

2018

J Raman Spectroscopy

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Flavins are cofactors in several light-activated enzymes and therefore their excited states are found to involve in many photobiological processes. Excited state dynamics of flavin compounds corresponding to their first singlet state (S 1 ) has been studied using a plethora of techniques, whereas studies related to highly absorbing ultraviolet excited states are lacking. Here, we study the ultrafast excited state dynamics of riboflavin and flavin mononucleotide using resonance Raman intensity analysis upon photoexcitation into their most intense absorption band centered at 266 nm. Resonance Raman cross sections of each flavin band are quantitatively measured across the 266-nm absorption band (257-280 nm), and Raman excitation profiles are constructed. We have used Lee and Heller's time-dependent wave packet theory to simulate the experimental Raman cross sections in a self-consistent manner. The simulation results in instantaneous structural changes along with solvation dynamics, through linewidth broadening within tens of femtoseconds following photoexcitation. Major structural changes were observed through contraction and elongation of several ring stretching coordinates, affecting at a different site when compared with the S 1 excitation. The value of the total reorganization energy was determined to be 1,665 cm −1 (and 1,602 cm −1 for flavin mononucleotide) with a contribution of 1,310 cm −1 from the inertial response of water. We find upon excitation, the first solvation shell inertially responds with an ultrafast timescale of <30 fs for both the molecules. Our results can be useful to determine the structure and dynamics of flavoenzymes by using flavin as a probe following excitation within their 266-nm absorption band.

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Section: Resultsmentioning

confidence: 64%

Deep ultraviolet initiated excited state dynamics of riboflavin and flavin mononucleotide

Ghosh

Puranik

2018

J Raman Spectroscopy

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“…The details, not described above, of our implementation of RT-TDDFT and LR-TDDFT gradients in NWChem can be found in the literature. 21,29 3. RESULTS AND DISCUSSION In order to demonstrate that meaningful information can be obtained with RT-TDDFT from an initially nonstationary density matrix, we have calculated ground-state absorption spectra of butadiene and an oligofluorene (H−(Fl) n −H) with two fluorene units.…”

Section: Methodsmentioning

confidence: 99%

Excited State Absorption from Real-Time Time-Dependent Density Functional Theory

Fischer

Cramer

Govind

2015

J. Chem. Theory Comput.

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The optical response of excited states is a key property used to probe photophysical and photochemical dynamics. Additionally, materials with a large nonlinear absorption cross-section caused by two-photon (TPA) and excited state absorption (ESA) are desirable for optical limiting applications. The ability to predict the optical response of excited states would help in the interpretation of transient absorption experiments and aid in the search for and design of optical limiting materials. We have developed an approach to obtain excited state absorption spectra by combining real-time (RT) and linear-response (LR) time-dependent density functional theory (TDDFT). Being based on RT-TDDFT, our method is aimed at tackling larger molecular complexes and materials systems where excited state absorption is predominantly seen and many time-resolved experimental efforts are focused. To demonstrate our method, we have calculated the ground and excited state spectra of H₂⁺ and H₂ due to the simplicity in the interpretation of the spectra. We have validated our new approach by comparing our results for butadiene with previously published results based on quadratic response (QR). We also present results for oligofluorenes, where we compare our results with both QR-TDDFT and experimental measurements. Because our method directly measures the response of an excited state, stimulated emission features are also captured; although, these features are underestimated in energy which could be attributed to a change of the reference from the ground to the excited state.

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“…All calculations were performed in a locally modified version of NWChem. 52,53 In addition to the LR and RT TD-DFT calculations of electronic excitations induced by the presence of point charges, NWChem was also used (unmodified) to optimize molecular geometries, calculate LR-TD-DFT excited state energy gradients, 54 and produce realspace electron density data for ground and excited states. 52 Atomic units (AU) have been used throughout this paper unless otherwise noted.…”

Section: Methodsmentioning

confidence: 99%

First Principles Determination of Electronic Excitations Induced by Charged Particles

Lingerfelt

Ganesh²,

Jakowski³

et al. 2019

Preprint

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A time dependent self consistent field based method for determining the rates of electronic excitations induced in materials by the presence of external point charges is presented. The method utilizes the full scalar potential of the external point charge in the interaction Hamiltonian instead of relying on multipolar expansions thereof. A general method is presented for determining the conditions under which dipole selection rules are adequate to describe the electronic response of the material to perturbation by external point charges. The position dependence of point charge induced transition rates between the ground and lowest few excited electronic states was resolved for a small polybenzoid. Notably, electronic excitations that are optically forbidden can be strongly allowed for particular positions of the perturbing point charge. Application of the methods detailed here can lead to an improved understanding of the electronic response of materials under irradiation by beams of charged particles.

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Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

Cited by 56 publications

References 130 publications

Deep ultraviolet initiated excited state dynamics of riboflavin and flavin mononucleotide

Deep ultraviolet initiated excited state dynamics of riboflavin and flavin mononucleotide

Excited State Absorption from Real-Time Time-Dependent Density Functional Theory

First Principles Determination of Electronic Excitations Induced by Charged Particles

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